Catalysis in organometallic CVD of thin metal films

• US 5,403,620 A
• Filed: 10/13/1992
• Issued: 04/04/1995
• Est. Priority Date: 10/13/1992
• Status: Expired due to Term

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Kaesz, Herbert D., Hicks, Robert F.
• Primary Examiner(s): Beck, Shrive
• Assistant Examiner(s): DANG, VI
• Application Number:
  US07/959,384
• Time in Patent Office: 903 Days
• Field of Search: 427/123, 427/124, 427/554, 427/255.2, 427/255.7, 427/252
• US Class Current: 427/252
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/44 characterised by the method of coating C23C16/04 takes precedence

Abstract

A process for CVD including plasma enhanced and laser induced CVD using one or more precursor film forming metal compounds as the major film forming metal precursor, for example organotungsten, which is admixed with minor amounts of a precursor catalytic metal compound, for example, an organoplatinum compound, as a precursor to a catalytic metal in the presence of hydrogen gas to provide improved purity of deposited metal films having residual amounts of the catalytic metal incorporated therein.

Claims

1. A process for the chemical vapor deposition of at least one metal onto a substrate comprising:

a) exposing said substrate to a fluid mixture containing a major amount of at least one vaporizable or soluble precursor film forming metal compound having the formula

space="preserve" listing-type="equation">L.sub.n MR.sub.m

and to a fluid containing a minor amount of at least one vaporizable or soluble precursor catalytic metal compound having the formula

space="preserve" listing-type="equation">L.sub.n M'"'"'R.sub.m

wherein L is a π

-bonding organic ligand consisting of ethylene, allyl, methylallyl, butadienyl, pentadienyl, cyclopentadienyl, methycyclopentadienyl, cyclohexadienyl, hexadienyl, cycloheptatrienyl, or alkyl or alkyl silyl or fluorinated derivatives of said precursor catalytic metal compounds having sufficient volatility of the precursor metal compound to be of utility in gaseous CVD or liquid CVD;

M is a precursor metal consisting of a transition metal, Ti (titanium), Zr (zirconium), Hf (hafnium), V (vanadium), Nb (niobium), Ta (tantalum), Cr (chromium), Mo (molybdenum), W (tungsten), Mn (manganese), Re (Rhenium), Fe (iron), Ru (ruthenium), Os (osmium), or a main group metal consisting of Al (aluminum), Ga (gallium), In (indium), a group 4a element consisting of Si (silicon), Ge (germanium), Sn (tin), or a lanthanide or actinide metal consisting of La (lanthanum), Nd (neodymium), Sm (samarium), U (uranium), Pu (plutonium;

M'"'"' is a metal selected from the group of metals that can catalyze hydrogenation and hydrogenolysis reactions of unsaturated and saturated organic ligands, L and R, to yield volatile byproducts and also can catalyze the hydrogenation of surface carbon to methane in the presence of hydrogen, and consisting of the Group VIII transition metals of Co (cobalt), Rh (rhodium), Ir (iridium), Ni (nickel), Pd (palladium), Pt (platinum), Fe (iron), Ru (ruthenium), and Os (osmium);

R is a σ

-bonding ligand radical consisting of hydrogen, methyl, ethyl, n- or iso- propyl, n-, sec-, or t- butyl, benzyl, phenyl, and silylated and fluorinated derivatives having sufficient volatility or solubility of the precursor metal compound to be of utility in CVD or liquid CVD;

n is a number from 0 to the valence of said metal,

m is a number from 0 to the valence of the metal, where m plus n allow a stable configuration of the precursor metal compound to allow the precursor compound to be either volatile or soluble in an organic solvent;

(b) exposing said substrate to hydrogen gas; and

(c) maintaining said substrate throughout the reaction at a temperature sufficiently high to decompose said precursor film forming metal compounds and said precursor catalytic metal compounds;

(d) reacting said precursor film forming metal compound and said precursor catalytic metal compound in the presence of hydrogen gas in a manner to cause decomposition of precursor metal compound L_n MR_m, and of the catalyst metal compound L_n M'"'"'R_m on the surface of said substrate to form on said surface a metal film M containing catalytic metal M'"'"' without causing substantial impurities from the ligands of said precursor compounds to be formed on said surface and incorporated on or within said metal film.

2. A process according to claim 1 wherein said precursor catalytic metal compounds L_n M'"'"'R_m comprise 0.1 to 10 mol % relative to said precursor film forming compounds L_n MR_m and both being introduced in a stream of inert gas.

3. A process according to claim 1 wherein said precursor film forming metal compounds comprise:

bis(cyclopentadienyl)dihydromolybdenum, (C₅ H₅)₂ MoH₂ ;

bis(cyclopentadienyl)(ethylene)molybdenum, (C₅ H₅)₂ MoC₂ H₂ ;

tris(butadiene)molybdenum, (C₄ H₆)₃ Mo;

tris(cyclobutadieny)molybdenum, (C₄ H₄)₃ Mo;

dicylopentadienyltrihydroniobium, (C₅ H₅)₂ NbH₃ ;

bis(cyclopentadienyl)niobiumborohydride, (C₅ H₅)₂ NbH₂ BH₂ ;

bis(cyclopentadienyl)hydro(ethylene)niobium, (C₅ H₅)₂ NbHC₂ H₂ ;

bis(cyclopentadienyl)allylniobium, (C₅ H₅)₂ NbC₃ H₄ ;

pentamethyltantalum, Ta(CH₃)₅ ;

bis(cyclopentadienyl)trihydrotantalum, (C₅ H₅)₂ TaH₃ ;

bis(cyclopentadienyl)trimethyltitanium, (C₅ H₅)₂ Ti(CH₃)₃ ;

titanocene borohydride, (C₅ H₅)₂ TiH₂ BH₂ ;

bis(cyclopentadienyl)dimethyltitanium, (C₅ H₅)₂ Ti(CH₃)₂ ;

bis(cyclopentadienyl)methylvanadium, (C₅ H₅)₂ VCH₃ ;

1,1'"'"'-dimethylvanadocene, (C₅ H₄ CH₃)₂ V;

bis(2,4-dimethylpentadienyl)vanadium, (C₅ H₃ (CH₃)₂)₂ V;

bis(cyclopentadienyl)dihydrotungsten, (C₅ H₅)₂ WH₂ ;

trisbutadienetungsten, (C₄ H₆)₃ W;

hexamethyl tungsten, (CH₃)₆ W; and

bis(cyclopentadienyl)(cyclobutadiene)zirconium, (C₅ H₅)₂ ZrC₄ H₄.

4. A process according to claim 1 wherein said precursor catalytic metal compounds comprise:

CpPtMe₃ ;

CpPt(allyl);

CpPt(methylallyl);

MeCpPt(methylallyl);

CpPt(CO)CH₃ ;

MeCpPt(CO)CH₃ ;

bisallylPd;

(methylallyl)Pd(allyl);

bis(2-methylallyl)palladium;

(cyclopentadienyl)(allyl)palladium;

(CH₃ C₅ H₄)PtMe₃ ;

(C₃ H₅)₃ Rh;

(C₃ H₅)₃ Ir;

CpIr(hexadiene);

(C₅ H₅)Ir(C₆ H₈);

(C₅ (CH₃)₅)Ir(ethylene)₂ ;

(C₅ H₇)Ir(C₈ H₈);

(CH₃ C₅ H₄)₂ Ni;

(cyclopentadienyl)(Cyclohexandienyl)cobalt, (C₅ H₅)Co(C₆ H₇);

(CH₃ C₅ H₄)Co(MeCp);

(C₅ H₅)CoCp;

(cyclobutadienyl)(cyclopentadienyl)cobalt, (C₄ H₄)Co(C₅ H₅);

bis(cyclopentadienyl)cobalt;

(C₅ H₅)₂ Co;

bis(methylcyclopentadienyl)cobalt, (CH₃ C₅ H₄)₂ Co;

cyclopentadienyl(1,3-hexadienyl)cobalt, (C₅ H₅)Co(C₆ H₇);

(cyclopentadienyl)(5-methyl-cyclopentadienyl)cobalt, (C₅ H₅)Co(C₅ H₄ CH₃);

(C₅ H₅)Co(CO)₂ ;

(C₆ H₈)CoCp;

bis(ethylene)s(pentamethylcyclopentadienyl)cobalt, ((CH₃)₅ C₅)Co(C₂ H₂)₂ ;

triallylchromium, (C₃ H₄)₃ Cr;

bis(cyclopentadienyl)chromium, (C₅ H₅)₂ Cr;

(cycloheptatrienyl)(cyclopentadienyl)chromium, (C₇ H₇)Cr(C₅ H₅);

bis(cyclopentadienyl)iron, (C₅ H₅)₂ Fe;

(2,4-cyclohexadienyl)(cyclopentadienyl)iron, (C₆ H₇)Fe(C₅ H₅);

(cyclopentadienyl)(methylcyclopentadienyl)iron, (C₅ H₅)Fe(C₅ H₄ CH₃);

bis(methylcyclopentadienyl)iron, (CH₃ C₅ H₄)₂ Fe;

(cycloheptatrienyl)(cyclopentadienyl) manganese, (C₅ H₅)Mn(C₇ H₈);

(benzene)(cyclopentadienyl)manganese, (C₅ H₅)Mn(C₆ H₆);

vinylosmocene, (C₅ H₅)Os(C₅ H₄ CHCH₂);

1,1'"'"'-dimethylosmocene, (C₅ H₄ CH₃)₂ Os;

ethylosmocene, (C₅ H₅ )Os(C₅ H₄ CH₂ CH₃);

bis(cyclopentadienyl)hydridorhenium, (C₅ H₅)₂ ReH;

hexamethylrhenium, (CH₃)₆ Re;

HRe(CO)₅ ;

cyclopentadienyl(methylcyclopentadienyl)ruthenium, (C₅ H₅)Ru(C₅ H₄ CH₃);

ruthenocenylacetylene, (C₅ H₅)Ru(C₅ H₄ CCH);

vinylruthenocene, (C₅ H₅)Ru(C₅ H₄ CHCH₂);

bis(methylcyclopentadienyl)ruthenium, Ru(CH₃ C₅ H₄)₂ ;

ethylruthenocene, (C₅ H₅)Ru(C₅ H₄ CH₂ CH₃).

5. A process according to claim 1 wherein said precursor film forming metal compounds comprise:

bis(cyclopentadienyl)dihydrotungsten, (C₅ H₅)₂ WH₂, or trisbutadienetungsten, (C₄ H₆)₃ W.

6. A process according to claim 1 further comprising:

annealing said deposited metal films to convert the metal films into a dense mat of small crystallites.

7. A process according to claim 1 wherein said precursor catalytic metal compound is CpPtMe₃ or MeCpPtMe₃.

8. A process according to claim 1 wherein said precursor catalytic metal compounds and said precursor film forming metal compounds are each mixed with an inert gas prior to introduction into said reaction chamber and wherein said precursor catalytic metal compounds/inert gas mixture, said precursor film forming metal compounds/inert gas mixture, and said hydrogen gas are directed in a continuous stream over said substrate.

9. A process according to claim 8 wherein said inert gas is mixed with said precursor catalytic metal compounds and with said precursor film forming metal compounds by separately passing a stream of said inert gas over each of said compounds to saturate said inert gas with said precursor catalytic metal compounds and with said precursor film forming metal compounds.

10. A process according to claim 1 wherein said substrate is heated to a temperature in the range of about 180°

C. to about 400°

C. and said reaction gases are at a temperature in the range of ambient to about 150°

C.

11. A process according to claim 1 wherein said substrate is comprised of a substance stable to the temperature and partial pressure of hydrogen and the temperature of the process.

12. A process according to claim 1 wherein two different precursor film forming metal compounds as defined in step (a) are included in the process to provide an alloy or mixture of two different metals having residual amounts of the catalytic metal deposited within the metal alloy or mixture.

13. A process according to claim 1 in which two or more different metals are deposited onto a substrate in a sequential process by following steps (a), (b), (c), and (d) to deposit the first layer of metal having a minor amount of the catalytic metal therein and then subsequently depositing another different metal on the first metal by repeating steps (a), (b), (c), and (d) of claim 1 until the total number of deposited metal layers has been formed.

16. A process according to claim 14 in which two or more different metals are deposited onto a substrate in a sequential process by following steps (a), (b), (c), and (d) to deposit the first layer of metal having a minor amount of the catalytic metal therein and then subsequently depositing another different metal on the first metal by repeating steps (a), (b), (c), and (d) of claim 1 until the total number of deposited metal layers has been formed.

14. A process for depositing at least one film of a metal onto a substrate comprising:

a) exposing said substrate to a gas or liquid mixture containing a major amount of at least one vaporizable or soluble precursor film forming metal compound having the formula

space="preserve" listing-type="equation">L.sub.n MR.sub.m

and to a fluid containing a minor amount of at least one vaporizable or soluble precursor catalytic metal compound having the formula

space="preserve" listing-type="equation">L.sub.n M'"'"'R.sub.m

wherein L is a π

-bonding organic ligand consisting of ethylene, allyl, methylallyl, butadienyl, pentadienyl, cyclopentadienyl, methycyclopentadienyl, cyclohexadienyl, hexadienyl, cycloheptatrienyl, or alkyl or alkyl silyl or fluorinated derivatives of said precursor catalytic metal compounds having sufficient volatility of the precursor metal compound to be of utility in CVD or liquid CVD;

M is a precursor metal consisting of a transition metal, Ti (titanium), Zr (zirconium), Hf (hafnium), V (vanadium), Nb (niobium), Ta (tantalum), Cr (chromium), Mo (molybdenum), W (tungsten), Mn (manganese), Re (Rhenium), Fe (iron), Ru (ruthenium), Os (osmium), or a main group metal such as Al(aluminum), Ga (gallium), In (indium), a group 4a element consisting of Si (silicon), Ge (germanium), Sn (tin), or a lanthanide or actinide metal consisting of La (lanthanum), Nd (neodymium), Sm (samarium), U (uranium), Pu (plutonium;

M'"'"' is a metal selected from the group of metals that can catalyze hydrogenation and hydrogenolysis reactions of unsaturated and saturated organic ligands, L and R, to yield volatile byproducts and also can catalyze the hydrogenation of surface carbon to methane in the presence of hydrogen, and consisting of the Group VIII transition metals of Co (cobalt), Rh (rhodium), Ir (iridium), Ni (nickel), Pd (palladium), Pt (platinum), Fe (iron), Ru (ruthenium), and Os (osmium);

R is a σ

-bonding ligand radical consisting of hydrogen, methyl, ethyl, n- or iso- propyl, n-, sec-, or t- butyl, benzyl, phenyl, and silylated and fluorinated derivatives having sufficient volatility or solubility of the precursor metal compound to be of utility in CVD or liquid CVD;

n is a number from 0 to the valence of said metal,

m is a number from 0 to the valence of the metal, where m plus n allow a stable configuration of the precursor metal compound to allow the precursor compound to be either volatile or soluble in an organic solvent;

(b) exposing said substrate to hydrogen gas; and

(c) exposing said substrate to irradiation from a laser beam at a wavelength sufficient to cause said precursor film forming metal compounds and said precursor catalytic metal compounds to react with said hydrogen gas; and

,

(d) depositing said metal films on the surface of said substrate without causing substantial heteroatom impurities from the organic portion of said precursor film forming metal compounds or from said precursor catalytic metal compounds to be formed on said surface.

15. A process according to claim 14 wherein step (c) comprises exposing said substrate to irradiation from a laser beam disposed at an incident angle from perpendicular to parallel to said substrate surface and at a wavelength sufficient to cause one or both of said precursor film forming metal compounds and said precursor catalytic metal compounds to react in the gas phase and in proximity to said substrate to react with said hydrogen on the substrate surface and deposit said metal film on the surface of said substrate.

17. A process according to claim 14 wherein one or more of the precursor metal compounds are selectively deposited to form a pattern.

18. In a process for depositing a metal film from a vaporizable or soluble precursor compound containing a metal to be deposited onto a substrate in the presence of hydrogen gas, the improvement which comprises:

exposing said substrate simultaneously or sequentially to at least one vaporizable or soluble precursor compound containing a metal which can be deposited as a metal film and a metal which can catalyze hydrogenation and hydrogenolysis reactions of unsaturated and saturated organic ligands to yield volatile byproducts and which can also catalyze the hydrogenation of surface carbon to methane in the presence of hydrogen to cause the metal from the catalyst compound to be incorporated within the deposited metal film as a dissolved portion, alloy, or at the metal surface, or at grain boundaries.

19. A process for controlling the amount of carbon in particular and oxygen in metal films produced by chemical vapor deposition on substrates comprising:

a) exposing said substrate to a fluid mixture containing a major amount of two or more vaporizable or soluble precursor film forming metal compounds having the formula

space="preserve" listing-type="equation">L.sub.n MR.sub.m

and to a fluid containing a minor amount of at least one vaporizable or soluble precursor catalytic metal compound having the formula

space="preserve" listing-type="equation">L.sub.n M'"'"'R.sub.m

wherein L is a π

-bonding organic ligand consisting of ethylene, allyl, methylallyl, butadienyl, pentadienyl, cyclopentadienyl, methycyclopentadienyl, cyclohexadienyl, hexadienyl, cycloheptatrienyl, or alkyl or alkyl silyl or fluorinated derivatives of said compounds having sufficient volatility of the precursor metal compound to be of utility in CVD or liquid CVD;

M is a precursor metal consisting of a transition metal, Ti (titanium), Zr (zirconium), Hf (hafnium), V (vanadium), Nb (niobium), Ta (tantalum), Cr (chromium), Mo (molybdenum), W (tungsten), Mn (manganese), Re (Rhenium), Fe (iron), Ru (ruthenium), Os (osmium), or a main group metal consisting of Al (aluminum), Ga (gallium), In (indium), Si (silicon), Ge (germanium), Sn (tin), or a lanthanide or actinide metal consisting of La (lanthanum), Nd (neodymium), Sm (samarium), U (uranium), Pu (plutonium;

M'"'"' is a metal selected from the group of metals that can catalyze hydrogenation and hydrogenolysis reactions of unsaturated and saturated organic ligands, L and R, to yield volatile byproducts and also can catalyze the hydrogenation of surface carbon to methane in the presence of hydrogen, and consisting of the Group VIII transition metals of Co (cobalt), Rh (rhodium), Ir (iridium), Ni (nickel), Pd (palladium), Pt (platinum), Fe (iron), Ru (ruthenium), and Os (osmium);

R is a σ

-bonding ligand radical consisting of methyl, ethyl, n- or iso- propyl, n-, sec-, or t- butyl, benzyl, phenyl, and silylated and fluorinated derivatives having sufficient volatility or solubility of the precursor metal compound to be of utility in CVD or liquid CVD;

n is a number from 0 to the valence of said metal,

m is a number from 0 to the valence of the metal, where m plus n allow a stable configuration of the precursor metal compound to allow the precursor compound to be either volatile or soluble;

(b) exposing said substrate to hydrogen gas; and

(c) maintaining said substrate throughout the reaction at a temperature sufficiently high to decompose said precursor film forming metal compounds and said precursor catalytic metal compounds;

(d) reacting said precursor film forming metal compounds and said precursor catalytic metal compounds in the presence of hydrogen gas in a manner to cause deposition of metals M from said two or more precursor film forming metal compounds, and of the catalyst metal M'"'"' from said precursor catalytic metal compounds on the surface of said substrate without causing substantial impurities from the organic portion of said precursor film forming metal compounds or of said precursor catalytic metal compounds to be formed on said surface and to be incorporated within said metal M layer.

20. A process according to claim 19 wherein M in each of said two or more precursor film forming metal compounds is different.

21. A process according to claim 19 wherein M in each of said two or more separate precursor film forming metal compounds is the same.

22. A process according to claim 19 wherein said deposition steps are simultaneous.

23. A process according to claim 19 wherein said deposition steps are sequential.

24. In a process for plasma-enhanced CVD of metal films wherein controlled amounts of one or more precursor film forming metal compounds in gaseous form are introduced into a reaction chamber in the vicinity of a heated substrate and wherein said precursor film forming metal compounds in gaseous form are exposed to a means for activating and sustaining a plasma contained and fed by said precursors in gaseous form, to cause deposition of a metal film on said substrate, the improvement which comprises:

adding controlled amounts of hydrogen gas and of at least one vaporizable precursor catalytic metal compound containing a metal which can catalyze hydrogenation and hydrogenolysis reactions of unsaturated and saturated organic ligands to yield volatile byproducts and which can also catalyze the hydrogenation of surface carbon to methane in the presence of hydrogen to cause the metal from the precursor catalytic metal compound to be incorporated within the deposited metal film as a dissolved portion, alloy, or at the metal surface, or at grain boundaries.

25. A process for the deposition of metal films of enhanced purity which comprises:

(a) forming a solution of a precursor catalytic metal compound having the formula;

space="preserve" listing-type="equation">L.sub.n M'"'"'R.sub.m

(b) wetting the surface of a substrate with said solution;

(c) evaporating solvent from said solution on said surface;

(d) heating said substrate in the presence of hydrogen gas to cause decomposition of said precursor catalytic metal compound and cause deposition of catalytic metal M'"'"' on the surface of said substrate without causing substantial impurities from the heteroatom portion of said precursor catalytic metal compound to be formed on said surface;

(e) exposing said substrate having said catalytic metal M'"'"' thereon to a fluid mixture containing at least one vaporizable or soluble precursor film forming metal M compound having the formula

space="preserve" listing-type="equation">L.sub.n MR.sub.m

wherein L is a π

-bonding organic ligand consisting of ethylene, allyl, methylallyl, butadienyl, pentadienyl, cyclopentadienyl, methycyclopentadienyl, cyclohexadienyl, hexadienyl, cycloheptatrienyl, or alkyl or alkyl silyl or fluorinated derivatives of said compounds having sufficient volatility of the precursor metal compound to be of utility in CVD or liquid CVD;

M is a precursor metal consisting of a transition metal, Ti (titanium), Zr (zirconium), Hf (hafnium), V (vanadium), Nb (niobium), Ta (tantalum), Cr (chromium), Mo (molybdenum), W (tungsten), Mn (manganese), Re (Rhenium), Fe (iron), Ru (ruthenium), Os (osmium), or a main group metal consisting of Al(aluminum), Ga (gallium), In (indium), a group 4a element comprising Si (silicon), Ge (germanium), Sn (tin), or a lanthanide or actinide metal consisting of La (lanthanum), Nd (neodymium), Sm (samarium), U (uranium), Pu (plutonium;

M'"'"' is a metal selected from the group of metals that can catalyze hydrogenation and hydrogenolysis reactions of unsaturated and saturated organic ligands, L and R, to yield volatile byproducts and also can catalyze the hydrogenation of surface carbon to methane in the presence of hydrogen, and consisting of the Group VIII transition metals of Co (cobalt), Rh (rhodium), Ir (iridium), Ni (nickel), Pd (palladium), Pt (platinum), Fe (iron), Ru (ruthenium), and Os (osmium);

R is a σ

-bonding ligand radical consisting of hydrogen, methyl, ethyl, n- or iso- propyl, n-, sec-, or t- butyl, benzyl, phenyl, and silylated and fluorinated derivatives having sufficient volatility or solubility of the precursor metal compound to be of utility in CVD or liquid CVD;

n is a number from 0 to the valence of said metal,

m is a number from 0 to the valence of the metal, where m plus n allow a stable configuration of the precursor metal compound to allow the precursor compound to be either volatile or soluble in an organic solvent;

(f) exposing said substrate to hydrogen gas; and

(g) maintaining said substrate throughout the reaction at a temperature sufficiently high to decompose said precursor metal compounds;

(h) reacting said precursor metal compound in the presence of hydrogen gas in a manner to cause deposition of metal M, on the surface of said substrate without causing substantial impurities from the organic portion of said precursor film forming metal compound or of said precursor catalytic metal compound to be formed on said surface and incorporated within said metal M layer.